Liquid Liquid Ion-Transfer Processes at the Dioctylphosphoric Acid (N,N-didodecyl-N',N'-diethylphenyle

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• 作者：Susan J. Stott ; Katy J. McKenzie ; Roger J. Mortimer ; Colin M. Hayman ; Benjamin R. Buckley ; Philip C. Bulman Page ; Frank Marken ; Galyna Shul ; and Marcin Opallo
• 刊名：Analytical Chemistry
• 出版年：2004
• 出版时间：September 15, 2004
• 年：2004
• 卷：76
• 期：18
• 页码：5364 - 5369
• 全文大小：282K
• 年卷期：v.76,no.18(September 15, 2004)
• ISSN：1520-6882

文摘

Biphasic electrode systems are studied for the case of theoxidation of the water-insoluble liquid N,N-didodecyl-N',N'-diethylphenylenediamine (DDPD) neat and dissolved in bis(2-ethylhexyl) phosphate (HDOP) and immersed in aqueous electrolyte media. The oxidationprocess in the absence of HDOP is accompanied bytransfer of the anion (perchlorate or phosphate) from thewater into the organic phase. However, in the presenceof HDOP, oxidation is accompanied by proton exchangeinstead. This electrochemically driven proton exchangeprocess occurs over a wide pH range. Organic microdroplet deposits of DDPD in HDOP at basal plane pyrolyticgraphite electrodes are studied by voltammetric techniques and compared in their behavior to organic microphase deposits in mesoporous TiO₂ thin films. Themesoporous TiO₂ thin film acts as a host for the organicliquid and provides an alternative biphasic electrode system compared to the random microdroplet/graphite system. Two types of mesoporous TiO₂ thin-film electrodes,(i) a 300-400-nm film on ITO and (ii) a 300-400-nmfilm on ITO sputter-coated with a 20-nm porous goldlayer, are investigated.